VOL. 3, NO.

3, JUNE 2008 ISSN 1819-6608

ARPN Journal of Engineering and Applied Sciences

2006-2008 Asian Research Publishing Network (ARPN). All rights reserved.

www.arpnjournals.com


EXTRACTION OF NEEM OIL (Azadirachta indica A. Juss) USING
N-HEXANE AND ETHANOL: STUDIES OF OIL QUALITY, KINETIC
AND THERMODYNAMIC

Maria Yuliana Liauw, F. A. Natan, P. Widiyanti, D. Ikasari, N. Indraswati and F. E. Soetaredjo
Department of Chemical Engineering, Widya Mandala Catholic University, Kalijudan, Surabaya, Indonesia
E-Mail: felyciae@yahoo.com

ABSTRACT
In this experiment, Neem oil extraction from Neem seeds (Azadirachta indica A. Juss) with n-hexane and ethanol
are presented. Effects of particle size, temperature and type of solvent on the extraction kinetic and thermodynamic
parameters were studied. Results showed that the maximum oil yields were 41.11% for ethanol and 44.29% for n-hexane at
50
o
C, and 0.425-0.71 mm particle size. Based on psycho-chemical characteristics analysis showed that increasing
temperature decreased iodine value but caused saponification, acid, and peroxide value became higher, which means
higher extraction temperature result on higher oil yield but lower oil quality. The kinetic of neem oil extraction was derived
from mass transfer rate equation. It also found that H is positive, S is positive, and G is negative indicating that
this process are endotermic, irreversible, and spontaneous.

Keywords: oil, neem, extraction, kinetic, thermodynamic.

INTRODUCTION
Neem (Azadirachta indica A. Juss) is one of the
very few trees known in the Indian subcontinent. This tree
is belonged to Meliceae family, and grows rapidly in the
tropic and semi-tropic climate. It is also observed that this
tree could survive in very dry and arid conditions. Neem
tree is an evergreen tree, but it may become leafless for a
short period in certain conditions [1]. Neem tree also
found in Indonesia in several areas such as Bali, Lombok,
West J ava, East J ava (Situbondo, Ngawi), Central J ava,
and Nusa Tenggara Barat. All parts of Neem plant such as
leaves, bark, flower, fruit, seed and root have advantages
in medical treatment and industrial products. Its leaves can
be used as drug for diabetes, eczema and reduce fever.
Barks of Neem can be used to make toothbrush. Neem
roots has an ability to heal diseases and against insects [1,
2]. However, this tree is not very popular in Indonesia
because it is only used as a canopy tree.
Neem seed is a part of Neem tree which has high
concentration of oil. Neem oil is widely used as
insecticides, lubricant, drugs for variety of diseases such
as diabetes and tuberculosis [1-3]. This oil could also
prolong leather goods when it is applied on them [1].
There are several methods to obtain Neem oil
from the seeds like mechanical pressing, supercritical fluid
extraction, and solvent extraction [1]. Mechanical
extraction is the most widely used method to extract Neem
oil from Neem seed. However, the oil produced with this
method usually has a low price, since it turbid and
contains a significant amount of water and metals
contents. Extraction using supercritical fluid, the oil
produced has very high purity; however the operating and
investment cost is high. Extraction using solvent has
several advantages. It gives higher yield and less turbid oil
than mechanical extraction, and relative low operating cost
compared with supercritical fluid extraction.
In this study we used solvent extraction to extract
the oil from Neem seed. The effects of parameter process
such as temperature and particle size were studied and
kinetic and thermodynamics model were developed. As
the solvents, we used ethanol and hexane.

MATERIALS AND METHODS

Material preparation
Neem seed used in this study were obtained from
Bali. This raw material has water content of 7.8% and oil
content of 49.58%. Prior to use, the Neem seeds were
repeatedly washed to remove dirt and other impurities
material, and subsequently dried in oven at 50C until it
reached constant moisture content. Then, Neem seeds
were ground to get three different particle sizes (0.85-1.40
mm, 0.71-0.85 mm, and 0.425-0.71 mm).

Oil extraction
Neem seeds were extracted using two solvent (n-
hexane and ethanol) for 3 hours with ratio Neem seed
powder weight to solvent volume of 1:5. In certain time
intervals, the samples were taken and centrifuged to
separate the solid fraction from solution. Filtrate was
heated and evaporated to obtain solvent-free oil. Then the
oil was weighed to calculate the concentration of oil in the
solution. Extractions were conducted at 5 temperature
level (30
o
, 35
o
, 40
o
, 45
o
and 50
o
C).

RESULTS AND DISCUSSIONS

Effect of temperature to quality of oil
Oil quality was affected by temperature,
hydrolysis, oxidation, lipase enzyme, and another
compounds in the oil. The effect of extraction temperature
to psychochemical characteristics of Neem oil is shown in
Figure-1.
49
VOL. 3, NO. 3, JUNE 2008 ISSN 1819-6608
ARPN Journal of Engineering and Applied Sciences

2006-2008 Asian Research Publishing Network (ARPN). All rights reserved.

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Temperature (C)
25 30 35 40 45 50 55
A
c
i
d

V
a
l
u
e

(
g
/
g
)
0
20
40
60
80
100
120
140
using n-hexane
using ethanol
Temperature (C)
25 30 35 40 45 50 55
S
a
p
o
n
i
f
i
c
a
t
i
o
n

V
a
l
u
e

(
m
g
/
g
)
0
50
100
150
200
250
using n-hexane
using ethanol

(a) (b)
Temperature (C)
25 30 35 40 45 50 55
P
e
r
o
x
i
d
e

V
a
l
u
e

(
m
g
/
g
)
0
2
4
6
8
10
using n-hexane
using ethanol

Temperature (C)
25 30 35 40 45 50 55
I
o
d
i
n
e

V
a
l
u
e

(
g
/
g
)
0
20
40
60
80
100
usingn-hexane
usingethanol

(c) (d)

Figure-1. The effect of Neem oil extraction temperature on (a) acid value; (b) saponification value;
(c) peroxide value; and (d) iodine value using n-hexane and ethanol.

The quality of Neem oil decreased as the
temperature increased. This is shown in Figure-1(a) to (d)
where the acid, saponification and peroxide value increase
while iodine value decrease. Acid value indicates the
amount of free fatty acids presents in an oil. Acid value is
good indicator of oil degradation caused by hydrolysis.
Figure-1(a) shows that higher extraction temperature
increased the acid value because the extraction
temperature influenced the hydrolysis of Neem oil [5-6].
Vegetable oil contains lipase enzyme which has an
optimum temperature about 35-40
o
C [7-9]. Lipase enzyme
hydrolyzes oil become free fatty acid and glycerol.
Saponification value indicates the average
molecular weight of triglycerides in the oil [5-6, 10].
Figure-1(b) shows that an increase in temperature,
increased the saponification value because higher
temperature caused lipid to breakdown therefore reduced
the average molecular weight of the oil [5, 10]. Peroxide
value is used as an indicator of oil rancidity [5]. Figure-
1(c) shows that an increase in temperature increased the
peroxide value. Increasing the temperature extraction
caused the oil to be rancid, thus leading to reduce its
oxidative stability. Rancidity is caused by aldehydes,
ketones, and oxidation [4, 11]. Iodine value expresses the
unsaturation level of the oil [9, 12]. Figure-1(d) shows that
higher temperature reduced the iodine value, since higher
temperature initiate the breakdown of carbon chain
bonding thus leading to form the saturated carbon chain.
This results on decrease the iodine value of oil.
The type of solvent did not affect on the
saponification and iodine value, however it influenced the
acid value. It implies that n-hexane as non-polar solvent
suitable for free fatty acid extraction compare to ethanol,
which is polar solvent, is able to extract bio-active
compounds [13].

Extraction kinetics
A relevant kinetic data is required to analyze and
design an extraction process especially in industrial scale.
In these experiments, we used mass transfer kinetic model
to represent our experiment data because there is no
reaction between the Neem oil with both solvent, n-hexane
and ethanol.
Neem oil, as an organic material, contains several
organic compounds such as nimbin, nimbidin, salannin,
etc. Since Neem oil is an organic material, it readily
dissolved in organic solvents like n-hexane and ethanol.
Here, the mechanism control for extraction of Neem oil in
n-hexane and ethanol is mass transfer, and we propose
mass transfer kinetic model to represent the yield data of
Neem oil extraction.
50
VOL. 3, NO. 3, JUNE 2008 ISSN 1819-6608
ARPN Journal of Engineering and Applied Sciences

2006-2008 Asian Research Publishing Network (ARPN). All rights reserved.

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For this model we assumed that the main
mechanism which controls the rate of Neem oil extraction
is mass transfer of Neem oil from Neem seeds (solid) to
bulk liquid n-hexane and ethanol. Mass transfer rate of
Neem oil from Neem seed to organic solvents can be
written as,

( )
A Ai
A
C C A k
dt
dW
= . .
(1)

Where dW
A
/dt is the mass transfer rate of neem oil (g/s),
C
A
and C
Ai
are the concentration of neem oil in bulk liquid
(organic solvents) at time t (g/L) and at equilibrium (g/L),
respectively. Here k is mass transfer coefficient and A is
surface area for mass transfer process. Since the extraction
was taken in batch process and its volume was kept
constant during process, therefore

( )
A Ai
A
W W
V
A
k
dt
dW
= . .
(2)
( )
A Ai
A
W W a k
dt
dW
= . .
(3)

Where k.a is volumetric mass transfer coefficient. To
solve Eq. (3), we used some conditions as follows:

At the beginning of extraction process (t =0), the
mass of Neem oil in bulk liquid is zero, W
A
=0.
At any time t, mass of Neem oil in bulk liquid is W
A
=
W
Ai
.

With those conditions, integration of Eq. (3) gives the
following result,

( ) [ ] t a k W W
Ai A
. . exp 1 = (4)

Eq. (4) can be rearrange so it can be written in terms of
yield per mass of Neem seed,

( ) [ ] t a k Y Y
Ai A
. . exp 1 = (5)

Where Y
A
andi Y
Ai
are yield of Neem oil in bulk liquid at
time t and at equilibrium per mass of Neem seed.

t (menit)
0 50 100 150 200
y
i
e
l
d

(
%
)
0
10
20
30
40
50
Time (min) vs Temperature (30C)
Time (min) vs Temperature (35C)
Time (min) vs Temperature (40C)
Time (min) vs Temperature (45C)
Time (min) vs Temperature (50C)

(a)
t (menit)
0 50 100 150 200
y
i
e
l
d

(
%
)
0
10
20
30
40
50
Time (min) vs Temperature (30C)
Time (min) vs Temperature (35C)
Time (min) vs Temperature (40C)
Time (min) vs Temperature (45C)
Time (min) vs Temperature (50C)

(b)
t (menit)
0 50 100 150 200
Y
i
e
l
d

(
%
)
0
10
20
30
40
50
Time (min) vs Temperature (30C)
Time (min) vs Temperature (35C)
Time (min) vs Temperature (40C)
Time (min) vs Temperature (45C)
Time (min) vs Temperature (50C)

(c)
Figure-2. Extraction kinetic of Neem seeds powder at
particle size (a) 0.85-1.40 mm; (b) 0.71-0.85 mm; (c)
0.425-0.71 mm using n-hexane as solvent.
Waktu (menit)
0 50 100 150 200 250
%

Y
i
e
l
d
0
10
20
30
40
50
Time (min) vs Temperature (30C)
Time (min) vs Temperature (35C)
Time (min) vs Temperature (40C)
Time (min) vs Temperature (45C)
Time (min) vs Temperature (50C)

(a)
Waktu (menit)
0 50 100 150 200 250
%

Y
i
e
l
d
0
10
20
30
40
50
Time (min) vs Temperature (30C)
Time (min) vs Temperature (35C)
Time (min) vs Temperature (40C)
Time (min) vs Temperature (45C)
Time (min) vs Temperature (50C)

(b)
51
VOL. 3, NO. 3, JUNE 2008 ISSN 1819-6608
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Waktu (menit)
0 50 100 150 200 250
%

Y
i
e
l
d
0
10
20
30
40
50
Time (min) vs Temperature (30C)
Time (min) vs Temperature (35C)
Time (min) vs Temperature (40C)
Time (min) vs Temperature (45C)
Time (min) vs Temperature (50C)

(c)
Figure-3. Extraction kinetic of Neem seeds powder at
particle size (a) 0.85-1.40 mm; (b) 0.71-0.85 mm; (c)
0.425-0.71 mm using ethanol as solvent.

Figures 2 and 3 shows the experimental kinetic data from
extraction of Neem oil in n-hexane and ethanol at various
temperatures and the fits of mass transfer kinetic model. In
these Figures, the experimental data are represented as
bullets and kinetic model as solid lines. In the kinetic
model, parameters Y
Ai
and k.a were estimated by the
nonlinear least square fit from Eq. (5) to experimental
data. Parameters from fitting of kinetic model are
summarized in Tables 1 and 2.






Table-1. Parameters fitting of Neem oil extraction kinetics using n-hexane.

0.85-1.40

mm 0.71-0.85 mm 0.425-0.71 mm
T
(
o
C)
Y
Ai

fitted
Y
Ai
experimental
k.a
Y
Ai

fitted
Y
Ai
experimental
k.a
Y
Ai

fitted
Y
Ai
experimental
k.a
30 35.8700 35.8901 0.3587 36.9500 36.9612 0.3695 38.0100 38.0266 0.3801
35 37.8300 37.8522 0.3783 38.5000 38.5585 0.3850 40.0000 40.0123 0.4001
40 39.1300 39.1514 0.3943 40.2100 40.2264 0.4021 41.6200 41.6302 0.4162
45 39.9800 39.9902 0.3998 41.4800 41.4983 0.4148 42.8800 42.8911 0.4287
50 41.0400 41.1429 0.4104 42.2900 42.3060 0.4228 43.7200 43.7263 0.4372

Table-2. Parameters fitting of Neem oil extraction kinetics using ethanol.

0.85-1.40

mm 0.71-0.85 mm 0.425-0.71 mm
T
(
o
C)
Y
Ai

fitted
Y
Ai
experimental
k.a Y
Ai
fitted
Y
Ai
experimental
k.a Y
Ai
fitted
Y
Ai
experimental
k.a
30 30.9760 33.43 0.0594 31.4472 33.6847 0.0635 32.4377 33.9500 0.0675
35 32.8000 34.85 0.0584 33.302 35.3500 0.061 33.7679 35.9500 0.0615
40 34.1317 35.63 0.0651 34.574 35.9883 0.0655 34.9842 36.6300 0.0711
45 35.6329 37.64 0.0774 36.0747 37.9400 0.0776 36.5482 38.5400 0.0777
50 37.2790 39.1733 0.109 37.7718 39.7733 0.1085 38.3562 41.0823 0.1083

Thermodynamic parameters
Thermodynamics parameters ( H , , and S G )
for the extraction of neem oil using n-hexane and ethanol
as solvents can be estimated using following equations,

R
S
T R
H
T R
G
K

+

=
1 1
ln



(6)
S
L
u
T
m
m
Y
Y
K = =



(7)
Where K is equilibrium constant, Y
T
is yield percent of oil
at temperature T, Y
u
is percent of oil remaining in Neem
seed, m
L
is amount of Neem oil in liquid at equilibrium
temperature T, m
S
is amount of Neem oil in solid at
equilibrium temperature T, R is gas constant, while H ,
S , and G are enthalpy, entropy, and free energy of
extraction, respectively.
The values of K and for extraction of Neem
oil using n-hexane and ethanol as solvents were calculated
using Eqs. (6) and (7) are given in Tables 3 and 4. The
values of enthalpy and entropy of extraction are given in
Table-5. The negative values of indicate that the
extraction of Neem oil using n-hexane and ethanol are
spontaneous process. The positive value of enthalpy
indicates that the process is endothermic and requires
energy during process.
G
G

52
VOL. 3, NO. 3, JUNE 2008 ISSN 1819-6608
ARPN Journal of Engineering and Applied Sciences

2006-2008 Asian Research Publishing Network (ARPN). All rights reserved.

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Table-3. Equilibrium constant of Neem oil extraction using n-hexane and ethanol.

Equilibrium constant (K)
0.85-1.40

mm 0.71-0.85 mm 0.425-0.71 mm
T
(K)
1/T
(1/K)
n-Hexane Ethanol n-Hexane Ethanol n-Hexane Ethanol
303 0.00330033 3.3872 4.3516 3.1268 4.5351 2.9447 4.7401
308 0.003246753 4.3930 5.5650 3.7434 6.1347 3.7062 6.9640
313 0.003194888 5.6973 6.4991 4.7115 7.0235 4.3930 8.1721
318 0.003144654 6.9588 10.840 5.6973 11.9598 4.8067 14.9827
323 0.003095975 8.4149 20.2028 6.5535 29.7037 5.5845 55.4572

Table-4. Free energy of Neem oil extraction using n-hexane and ethanol.

G (J /mol)
0.85-1.40

mm 0.71-0.85 mm 0.425-0.71 mm
T
(K)
1/T
(1/K)
n-Hexane Ethanol n-Hexane Ethanol n-Hexane Ethanol
303 0.00330033 -2663.0574 -4298.1595 -2759.5630 -4425.2737 -3252.0303 -4562.6751
308 0.003246753 -3336.3060 -5158.0664 -3232.9716 -5485.8683 -3515.1134 -5928.8767
313 0.003194888 -3714.3888 -5777.2473 -3910.6174 -6056.1254 -4413.4913 -6627.2622
318 0.003144654 -3962.3262 -7951.8484 -4137.4696 -8437.8957 -5054.1845 -9763.0717
323 0.003095975 -4298.2758 -12855.1204 -4723.4840 -13370.9323 -5451.8852 -16968.0632

Table-5. Enthalpy and entropy of Neem oil extraction using n-hexane and ethanol at various particle size.

H (J /mol) S (J /mol)
Particle size
(mm)
n-Hexane Ethanol n-Hexane Ethanol
0.85-1.40
37.03
115505.1730
0.13
392.0458
0.71-0.85
31.02
86687.0813
0.11
299.2475
0.425-0.71
25.33
75340.2695
0.09
263.7695

CONCLUSIONS
The maximum yield obtained from extraction of
neem oil research were 44.29% for n-hexane and 41.11%
for ethanol at 50C and 0.425-0.71 mm particle size.
Based on psycho-chemical characteristics analysis,
increasing temperature decreased iodine value but
increased saponification, acid, and peroxide value which
means increasing temperature increased neem oil yield but
decreased neem oil quality. This extraction follows first
order kinetic with smaller value as decrease of
temperature. It also found that
a k.
H is positive, S is
positive, and is negative indicating that this process
are endotermic, irreversible, and spontaneous.
G

ACKNOWLEDGEMENTS
The authors are grateful for the financial support
from TPSDP (Technological and Professional Skills
Development Sector Project, ADB Loan No. 1792-INO)
from Chemical Engineering Department of Widya
Mandala Catholic University Surabaya, Indonesia.

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VOL. 3, NO. 3, JUNE 2008 ISSN 1819-6608
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2006-2008 Asian Research Publishing Network (ARPN). All rights reserved.

www.arpnjournals.com


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54